Surface chemistry and buried interfaces in all-inorganic nanocrystalline solids


Semiconducting nanomaterials synthesized using wet chemical techniques play an important role in emerging optoelectronic and photonic technologies. Controlling the surface chemistry of the nano building blocks and their interfaces with ligands is one of the outstanding challenges for the rational design of these systems. We present an integrated theoretical and experimental approach to characterize, at the atomistic level, buried interfaces in solids of InAs nanoparticles capped with Sn2S64– ligands. These prototypical nanocomposites are known for their promising transport properties and unusual negative photoconductivity. We found that inorganic ligands dissociate on InAs to form a surface passivation layer. A nanocomposite with unique electronic and transport properties is formed, that exhibits type II heterojunctions favourable for exciton dissociation. We identified how the matrix density, sulfur content and specific defects may be designed to attain desirable electronic and transport properties, and we explain the origin of the measured negative photoconductivity of the nanocrystalline solids.

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Fig. 1: Measured electronic and optical properties of layers of 4.5 nm InAs NCs capped with Sn2S64– ligands.
Fig. 2: Calculated interface energies between InAs(001) and Sn2S64– ligands.
Fig. 3: X-ray photoemission and Raman spectra of InAs NPs.
Fig. 4: MD simulations of InAs NCs embedded in SnxSy matrices.
Fig. 5: Isodensity plots of the square wavefunction moduli for representative defect states of InAs NCs interfaces with amorphous matrices.
Fig. 6: Band alignment and defect states at the nanoparticle–matrix heterojunction as a function of S content.
Fig. 7: Model of ambipolar photoresponse of InAs NCs with Sn2S64– ligands.


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V. Kamysbayev helped with the elemental analysis of the samples. V.S. was primarily supported by the University of Chicago Materials Research Science and Engineering Center, funded by NSF under award no. DMR-1420709. G.G., E.J. and D.T. were supported by MICCoM as part of the Computational Materials Sciences Program funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division (5J-30161-0010A). E.S. and S.W. were supported by the German Ministry of Education and Research (BMBF) within the NanoMatFutur programme, grant no. 13N12972. Supercomputer time provided by NERSC (project no. 35687) and the Max-Planck Computing and Data Facility, Garching, is acknowledged.

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S.W. and G.G. conceived and designed the calculations. E.S. performed the calculations. D.T. conceived and designed the experiments. V.S. and E.J. performed the experiments. The manuscript was written by D.T., G.G. and S.W. All the authors discussed the results and commented on the manuscript.

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Correspondence to Stefan Wippermann.

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Scalise, E., Srivastava, V., Janke, E. et al. Surface chemistry and buried interfaces in all-inorganic nanocrystalline solids. Nature Nanotech 13, 841–848 (2018).

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